Derivatives of 1, 4-bismethylene cyclohexane and 1, 4-bismethylene cyclohexadiene and processes of preparation



United States Patent ()fiice 3,115,506 DERWATHVES 6F Ld-BRSMETHYLENECYQLG- TEXANE AND lA-BTSMETHYLENE QYQLQHEX- ADENE AND PRUQESSES 6FPREPARATTQN Donald S. Asher and Daie C. Blomstram, Wilmington,

Del, assignors to E. l. du Font de Nenreurs and Cempany, Wilmington,Del, a corporation of Delaware No Drawing. Filed Mar, 23, 196i Ser. No.17,753 14 Claims. (til. 260396) This invention relates to a new class ofchemical compounds and to their preparation and more particularly to1,4-bis(disubstitutedmethylene)cyclohexanes, -cyclo hexadienes,-alkylcyclohexanes, and -alkylcyclohexadienes. The invention alsocomprises the amine and alkali and alkaline earth metal organic oxidecondensation products of tetracyanoquinodirnethane and C-allyltetracyanoquinodimethanes, i.e.,1,4-bis(dicyanomethylene)cyclohexadiene and l,4-bis(dicyanomethyle-e)alkylcyclohexadienes.

This application is a continuation-in-part of our copending applicationsSerial No. 762,282, filed September 22, 1958, and Serial No. 826,135,filed July 10, 1959, now abandoned.

The thermographic process for copying of printed or Written records usesa copy sheet bearing a substantially colorless coating which darkens onheating. When such a sheet is placed in contact with a text-bearingmaster and the assembly is exposed to a source of radiant heat, theportions of the copy sheet in register with text areas, particularlyWhere they contain carbon, are heated much more rapidly than portions inregister with blank areas of the master. The copy sheet is darkened onlyin those areas in register with text areas of the master and a copy isobtained. The color change in the copy sheet must take place at atemperature which otherwise causes no change in the copy sheet ormaster.

We have now found that 1,4-bis(disubstitutedmethylene)cyclohexanes and-cyclohexadienes are especially suitable as active ingredients inthermographic copying papers of the type described above. These new anduseful compounds can be prepared by the condensation of1,4-cyclohexanediones with a disubstitutedmethylene compound to yield1,4-bis(disubstitutedmethylene)cycolhexanes, which by oxidation can beconverted to the corresponding 1,4-bis disubstitutedmethylenecyclohexadienes. The susbtituents in the disubstitutedmethylene moietiesare carboxyl groups and groups hydrolyzable to carboxyl.

The products of this invention can be illustrated as follows:

" 3,115,506 rienrsa Dec. 24, 1963 The preferred embodiments for Q Q Qand Q include COOR CONR R COX, and CN, where R is hydrogen or alkyl of 1to 8 carbons and R R and R are hydrogen or hydrocarbyl groups containingup to 30 carbon atoms, and preferably up to 10 carbon atoms each, and Xis halogen, i.e., fluorine, chlorine, bromine, or iodine.

The process of this invention can be illustrated as follows:

where the Qs are as defined above.

In the step of condensing 1,4-cyclohexanediones with a disubstitutedmethylene compound, the presence of a catalyst is necessary. Thecatalyst can be an acid or a base, or a salt which ionizes in water togive an acidic or basic solution. Thus there can be employed any of theWide variety of catalysts that have been shown useful in the Knoevenageland aldol condensations. Active cata lysts include iydrochloric acid,sodium and potassium carbonates, sodium and potassium cyanides, sodiumacetate, ammonium acetate, piperidinium acetate, sodium bisulfite,sodium hydroxide, trisodium phosphate, diethylamine, Zinc chloride,sodium rnethoxide, acidic or basic ion exchange resins, pyridine,piperidine, and the like.

In the condensation step, water is always formed, and yields aresometimes improved if it is removed. This can be done by means ofdehydrating agents, by simple distillation, or by refluxing the reactionmixture in the presence of an inert organic liquid immiscible withwater, such as a hydrocarbon, and separating the water from the refluxcondensate.

The step of oxidizing the 1,4-bis(disubstitutedmethylene)cyclohexanes tothe corresponding cyclohexadienes can be carried out by directoxidation, such as by the action of air, oxygen, a peroxide, or anydirect chemical oxidant, or it can be carried out indirectly byhalogenating and dehydrohalogenating as indicated in. the followingequation:

where X is chlorine or bromine. Alternatively the halogenation can becarried out by a halogenating agent such as, for instance,N-bromosuccinimide, phosphorus pentabromide, phosphorus pentachloride,and the like.

In the following illustrative examples, parts are by weight unlessotherwise indicated. Example I represents a preferred embodiment of theinvention.

EXAMPLE I Part A.1,4-Bis(Dicyanomethylene) Cyclohexane A mixture of 140parts of malononitrile, 112 parts of 1,4-cyclohexaned-ione, 63 parts ofacetic acid, and 20 parts. of ammonium acetate in 1760 parts of benzeneis heated under reflux using a water separator 'for about two hours oruntil the theoretical amount of Water has been removed. The reactionmixture is cooled and the solid product which precipitates is collectedby filtration and washed well with water. Recrystallization from ethylacetate gives 159 parts (76.5% yield) of1,4-bis(dicyanometl1ylene)cyclohexane, MP. 197212 C. A sample foranalysis is prepared by several recrystallizations from ethyl acetate,MP. 204210 C.

Analysis.Calcd. for C H N C, 69.2; H, 3.9; N, 26.9. Found: C, 69.4; H,4.1; N, 26.3.

Another and preferred technique in view of the noticeably higher yieldsand greater purity of the product therein obtained is illustrated in thefollowing:

In an open glass reactor of internal capacity corresponding to 1,000parts of water was placed 100 parts of 1,4- cyclohexanedione and 119parts of malononitrile. The mixture was heated at steam bathtemperatures until significant melting had occurred, at which point asolution of one part of ,B-alanine in 200 parts of water was added. Thereaction vessel was heated at steam bath temperatures with occasionalswirling until the formation of a few crystals was noted, at which pointheating was discontinued. An exothermic reaction then began, and, whenit had become sufficiently vigorous to cause the reaction mixture toboil, the reactor was placed in an ice/ water bath until boiling hadceased, at which point the reactor and the still warm reaction mixturewere removed from the cooling bath and allowed to stand until it hadcooled essentially to room temperature. The nearly solid mas was thenfiltered and washed with water until the washings were colorless. Thefilter cake was air-dried and then washed with diethyl ether until thewashings were colorless. After air-drying, there was thus obtained 180parts (97% of theory) of 1,4-bis(dicyanomethylene)cyclohexanc as whitecrystals melting at 2l6217 C.

Part B.1,4-Bis(Dicyanmcthylene)Cyclohexadielze, i.e.,7,7,8,8-Tetracyan0quin0dimethane (TCN Q) A solution of 76.5 parts of1,4-bis(dicyanomethylene)- cyclohexane in 1174 parts of acetonitrile isstirred at 50 C. under a nitrogen atmosphere while 160 parts of N-bromosuccinimide is added in small portions over a 45- rninute period.The reaction mixture is stir-red at the same temperature for anadditional 45 minutes. It is then chilled to 20 C. and a solution of 72parts of pyridine in 714 parts of ether is added. After the reactionmixture is stirred at to C. for an additional 15 minutes, it is allowedto warm to room temperature. Cold Water is added and the precipitatewhich forms is collected by filtration and recrystallized from ethylacetate to give 641 parts (84% yield) of rust-colored crystals of1,4-bis(dicyanomethylene) cyclohexadiene, Ml. 239-291 C. (dec). A samplefor analysis is prepared by recrystallization from ethyl acetate. Thisproduct can be sublimed under high vacuum at 200 C. with 97% recovery.It sublimes, apparently unchanged, when heated above 250 C. atatmospheric pressure. When a few crystals are crushed between microcover glasses and heated on a Fisher melting point block, a deep bluefilm forms on the glass plates starting at about 200 C.

Analysis.Calcd. for C H N C, 70.6; H, 2.0; N, 27.4. Found: C, 71.3; H,2.0; N, 28.2. v

Another technique for the halogenation/dehydrohalogenation procedureusing a halogen directly as the halogenating reagent is illustrated inthe following, which procedure generally results in a slightly purerproduct as evidenced by the higher melting point.

A mixture of 12 parts of 1,4-bis(dicyanomethylene)- cyclohexane, 156parts of acetonitrile, and 19.2 parts of bromine in a glass reactor wascooled with stirring using an external ice/Water oath to 10 C. under anatmosphere of nitrogen. The reaction vessel was maintained in the ice/water bath, and a solution of 18.8 parts of pyridine in 23.5 parts ofacetonitrile was added over a period of 15 minutes with continuedstirring at such a rate that, with continued external cooling, thetemperature of the reaction mixture remained at 0 C. The reactionmixture was then stirred an additional minutes at 0 C., at which pointthe cooling bath was removed and the reaction mixture allowed to warm to20 C. over a period of one hour, at which point 300 parts of cold waterwas added and the resultant solid removed by filtration. The filter cakewas washed with Water and air-dried, thereby affording 12.1 parts ofcrude TCNQ as a yellow solid melting at 293295 C. with decomposition.After recrystaLlization from acetonitrile, there was obtained 9.3 partsof theory) of pure TCNQ as rust-colored crystals melting at 293.5296.0C.

As stated expressly in the foregoing, the present invention is genericto the 1,4-bis(disubstitutedmethylene)cyclohexanes, -cyclohexadienes,-alkylcyclohexanes, and -alkylcyclohexadienes. The immediately foregoingexamples have illustrated in detail the preparation of a representative1,4-bis(disubstitutedmethylene)cyclohexane and a representative 1,4-bisdisubstitutedmethylene) cyclohexadiene. Application of substantially thesame techniques, utilizing disuostituted C-alkylcyclohexane reactants,results in the formation of the corresponding1,4-bis(disubstitutedmethylene)alkylcyclohexanes and-alkylcyclohexadienes. More specifically:

Part C.-2-Zl Iethyll,4-Bis (Dicyanomethylene Cycloh exane To 43 parts of2rnethyl-1,4-cyclol1exanedi0ne was added 4 6.2 parts of malononitrileand 0.5 part of fi-alanine dissolved in five parts of water. The mixturewas heated for two hours at steam bath temperatures and then let standovernight at room temperature. The solid product was washed with waterand then with diethyl ether and subsequently air-dried. There was thusobtained 54 parts (71% of theory) of crystallineZ-methyl-lA-bis(dicyanomethylene)cyclohexane melting at 186-194" C.after recrystallization from ethyl acetate. The infrared spectrum of theproduct Was wholly consistent with the Z-methyl-1,4-bis(dicyanomethylene)cyclohexane structure. The product exhibited asingle absorption band in the ultraviolet region at 249 111,14 with anextinction coefllcient of Analysis.Calcd. for C H NL C, 70.2%; H, 4.5%;N, 25.2%. Found: C, 70.1%; H, 4.8%; N, 25.0%.

To a solution of parts of Z-methyl-l,4-bis (dicyanomethylene)cyclohexaneand 28.8 parts of bromine in 299 parts of acetonitrile cooled with anexternal ice/ salt bath was added 28.3 parts of pyridine slowly over aperiod of about twenty minutes with stirring while maintaining theexternal cooling. After the addition was complete, the reaction mixturewas stirred for an additional one-half hour with cooling and then fortwo more hours at room temperature, at the end of which time 555 partsof cold water was added. The resultant solid product was removed byfiltration and washed with 23{) parts of cold water. The crude2-methyl-7,7,8,S-tetracyanoquinodimethane (MeTCNQ) was dissolved in 766parts of acetonitrile. After filtration, the filtrate was heated withdecolorizing charcoal, filtered, and cooled to room temperature. Theresultant clear filtrate was concentrated to a volume corresponding to50 parts of water under a stream of nitrogen. On filtration andair-drying, there was thus obtained 3.6 parts (18% of theory) of pureMeTCNQ as dark tan microcrystals melting at 193-195 C. and exhibiting asingle absorption maximum in the ultraviolet region at 396 me with anextinction coetiicient of 45,668. The infrared spectrum was whollyconsistent with the MeTCNQ structure.

Analysis.-Calcd. for C H N C, 71.5%; H, 2.8%; N, 25.7%. Found: C,71.3%;1-1, 3.4%; N, 25.8%.

The C-alkyl-l,4-cyclohexanediones from which the 1,4-bis(disubstitutedmethylene)alkylcyclohexanes and -alkylcyclohexadienesof the present invention are prepared, as per the preceding Example 1,Parts C and D, are themselves conveniently obtained by the Birchreduction with sodium and liquid ammonia in ethanol of the diethers ofthe corresponding C-alkylhydroquinones, some of which are availablecommercially, in accord with the following stoichiometry, using dimcthylsulfate and accordingly the dimethyl ether as illustrative.

or-r OOH:

R onuisoi R No I on corn ooni fi 1+) R FR aqueous R R R I R acid R R U0cm 0 EXAMPLE II A mixture or" 234 parts of 1,4-bis(dicyanomethylene)-cyclohexane and 222 parts of selenium dioxide in 3,914 parts ofacetonitrile is heated under reflux for six hours and filtered hot toremove any insoluble material. The solvent is then removed byevaporation under reduced pressure. A solid residue remains which isrecrystallized from ethyl acetate and then sublimed to yield 45 parts of1,4-bis(dicyanomethylene)cyclohexadiene. After recrystallization of thissublimed product from ethyl acetate, a product melting at 290292 C.(Cleo) is obtained.

By substitution of other active methylene compounds for malononitrile inthe condensation with 1,4-cyclohexanedione as shown in Example 1, other1,4-bis(disubstitutedrnethylene)cyclohexanes and the corresponding 1,4-

bis(disubstitutedmethylene)cyclohexadienes of this invention can beprepared as shown in the following table:

TABLE Active Methylene lA-bis (disubstituted- 1,4-bis (disubstitutod-Compound Inethylcnc)cyclohcxanc methylene)- cyclohexadicnc Dlethylmelon-ate.-. 1,4-bis (diethoxy-car- 1,4-bis(diethoxycarbonylmethylcne)bonylnlethylcnc) cyclohexane. cyclohcxadicne.

Malonamidc Libisklicarbarnoyl- 1,4-bistdicarlmmoylmcthy1enc)cycl0-methyienc cyclohexane. hexadicne.

Ethyl cyanoacetate. 1,4-bis(cyano(ethoxy 1,4-bis(cyano(ethoxycarbonyl)methylene) carbonyl) methylcyclohexanc. cnc)cyclohexa- (licno.

Cyauoacctamide 1,4-bis(carbamoyl- 1,4bis(carbamoylcyanoulethylcnc)cyanorncthylcnc) cyclohexane. cyclohexadiene.

The products of this invention can also be prepared by other means. Forexample, 1,4-b1s(d1cyanomethylene)cyclohexane can be hydrolyzed by theaction of conceutrated solutions of sulfuric acid or sodium. hydroxide.By adjusting the time of the hydrolysis reaction and the concentrationof the solution, products can be prepared in which one, two, three, orfour of the cyano groups are hydrolyzed to carboxyl groups. In a similarway, 1,4-bis (dicyanomethylene)cyclohexadiene can be partly orcompletely hydrolyzed to the corresponding carboxylic acid derivatives.

These carboxylic compounds are converted to the corresponding acidchlorides by reaction with thionyl chloride. The acid chlorides areconverted to the corresponding acid fluorides, bromides, or iodides byinterchange with hydrogen fluoride, hydrogen bromide, or hydrogen iodidein the presence of the corresponding alkali metal halide salt, as shownby Wagner and Zook in Synthetic Organic Chemistry, John Wiley & Sons,1953, method 338, page 548. For example,1,4abis(dicarboxymethylene)cyclohexane reacts with thionyl chloride toyield 1,4- bis(di(chlorocarbonyl)methylene)cyclohexane which can betreated with sodium hydrogen fluoride to yield 1,4-bis(di(fluorocarbonyl)rnethylene)cyclohexane or with sodium hydrogenbromide to yield 1,4-bis(di(bromocarbonyl)methylene)cyclohexane. Thecorresponding 1,4-bis (di(halocarbonyl)methylene)cyclohexadienes can besimilarly prepared from 1,4-bis(dicarboxymethylene)cyclohexadiene.

The use of the 1,4-bis(disubstitutedmethylene)cyclohexanes and 1,4bis(disubstitutedmethylene)cyclohexadienes of this invention forpreparing thermographic images is illustrated as follows:

A hot solution of about four parts ofl,4-bis(dicyanomethylene)cyciohexadiene in about 600 parts of dioxane isbrushed onto photographic paper stock. After the coated paper is driedat room temperature, it is pressed for five seconds against metal reliefimages (nickel foiled electrotype) heated at various temperatures. Withthe relief image at C. a faint brownish yellow image is formed. With therelief image at 188 200 C. a deep brown image is obtained. Under similarconditions, uncoated photographic paper does not give any colorationwhen pressed against hot metal relief images.

The 1,4-bis (disubstitutedmethylene)cyclohexadienes of this inventionare also useful for reducing to the corresponding1,4bis(disubstitutedmethyl)benzenes. This may be illustrated as follows:

A solution of 1,4-bis(dicyanomethylene)cyclohexadiene in glacial aceticacid is treated with a molecular excess of thiophenol and allowed toevaporate to dryness. The residue is extracted with ether, and theremaining solid is recrystallized from ethanol to yield1,4-bis(dicyanomethyhbenzene melting at 244245 C.

AnaZysis.Calcd. for C H N C, 69.9; H, 2.93; N, 27.2. Found: C, 70.14; H,2.97; N, 27.45.

As another example, a mixture of 41 parts of 1,4-

7 bis(dicyanomethylene)cyclohexadiene, 80 parts of mercaptoacetic acid,and 1049 parts or glacial acetic acid is: heated at reflux under anitrogen atmosphere for 15 min-- utes. When the hot reaction mixture isdiluted with 1000' parts of water and then cooled in ice,1,4-bis(dicyanomethyl)benzene crystallizes as white needles. After theproduct has been washed with water and dried, it. weighs 36 parts (80%yield) and melts at 24l243 C.

The 1,4bis(disubstitutedmethyl)benzenes can also be: interconverted. Forinstance, refluxing of 0.3 part of the above1,4-bis(dicyanomethyl)benzene (which also can betermedp-phenylenedimalononitrile), for 3.5 hours with. 24 parts of methanolcontaining 0.173 part of water while passing a rapid stream of dryhydrogen chloride gas. through the solution, resulted in hydrolysis ofthe nitrile groups and conjoint esterification of the resulting car--boxylic acid groups. Dilution of the reaction mixture with. waterafforded 0.783 parts (79% of theory) or" 1,4-bis-[di(methoxycarbonyl)methyl]benzene, i.e., n-phenylenebis(dimethylmalonate), as a granular crystalline precipi-- tate melting at 149-15lC. Repeated recrystallization from benzene/pentane mixtures resulted inraising the melting point to l51.5 C. to 152.0 C.

Analysis.--Caicd. for C H O C, 56.8%; H, 5.4%- Found: C, 56.8%, H, 5.4%.

The 1,4 bis(disubstitutedmethylene)cyclohexadienes can also be preparedby suitable dehydrogenation of the 1,4bis(disubstitutedmethyl)benzenes.Thus, a solution of 0.96 part of the above p-phenylenebis(dirnethylmalonate), 0.35 part of sdoium methoxide, and 79 parts of methanol wasrefluxed under nitrogen for 1.25 hours, and the reaction mixture wasthen evaporated to dryness under reduced pressure. The residue wascovered with about 50 parts of benzene and iodine was added slowly withswirling until a permanent iodine color remained in the benzene solution(approximately 0.3 part of iodine was required). The reaction mixturewas filtered, and the filter cake was slurried with an aqueous solutionof potassium iodide and sodium bisulfite to remove excess iodine. Themixture was filtered, and the filter cake was washed first with waterand then with hexane. There was thus obtained as a yellow-green solid0.245 part (26% of theory) of crude 1,4-bis[di(methoxycarbonyl)methyl]cyclohexadiene, which can also be referred to ascyclohexa-2,5-diene-l,4-diylidenebis(dimethyl malonate), and moreconcisely as 7,7,8,8-tetra-(methoxycarbonyl)quinodimethane. Onrecrystallization, the purified 7,7,8,8-tetra(methoxycarbonyl)quinodimethane was obtained as bright yellow, prismaticneedles which did not exhibit a distinct melting point but appeared togradually polymerize on heating. The compound exhibited a singleabsorption band in the ultraviolet region at 368 m with an extinctioncoefiicient of 47,000.

Analysis.Calcd. for C H O C, 57.1%; H, 4.8%. Found: C, 57.5%; H, 4.9%.

The 1,4-bis(disubstitutedmethyl)benzenes can also be prepared by othermethods, as illustrated below.

To the alcohol-free sodium ethoxide from 12 parts of sodium there isadded 293 parts of ethyl carbonate, 87 parts of toluene, and 39 parts ofp-xylylenedicyanide. This mixture is heated with stirring until material(mostly ethanol) be ins to distill through a distilling column attachedot the reactor. Toluene is added to the reaction mixture at the samerate that distillate is collected until the head temperature reaches 115C. This process requires the addition of about 2l7 parts of toluene. Tothe cooled reaction mixture there is added 300 parts of water and 42parts of glacial acetic acid. The oil that separates is collected, andthe aqueous phase is extracted with two 7l-part portions of ether. Thecombined oil and ether extracts are dried over magnesium sulfate andfreed of volatile material by distillation at 15 mm. pressure at Sl00 C.The oil that remains is distilled, and the portion that boils at 223C./2.7 mm. to 231 C./2.0 mm. is collected. The resulting 1,4-bis (cyano(ethoxycarbonyl)methyl)benzene Weighs 33 parts (44% yield) andcrystallizes slowly to a moist solid when stored at room temperature.The infrared spectrum of this material shows bands at 4.45 microns (CEN)and 5.72 microns (ester C=O). When an ethanol solution of this materialis mixed with ammoniacal silver nitrate, a silver mirror forms, and thesolution develops a deep blue color.

The usefulness of the 1,4-bis(disubstitutedmethyl)benzcnes asphotographic developers is illustrated in the following paragra' h.

A photographic developer solution is prepared by dissolving one part of1,4-bis(dicyanomethyhbenzene in 1009 parts or 5% aqueous sodiumbicarbonate solution containing one part of potassium bromide. A stripof positive photographic emulsion is exposed under a stepln 2.otographic dark room the exposed film is immersed in the above developersolution for four minutes. It is then fixed in hypo and washed byconventional photographic procedures. The developed strip shows adensity gradation corresponding to the variation of exposure under thestepwedge and good differentiation between exposed and unexposed areasof the emulsion.

As given in detail in the foregoing Example I, Parts C and D, for thespecific Z- methylsubstituted-1,4-bis(disub- :stituted) cyclohexane and-cyclohexadienes there involved, viz., the bis(dicyanomethylene)compounds, the preparative techniques therefor are substantiallyidentical with those given in detail in the preceding discussions for Itis compounds without the alkyl substituent. In similar flash-ion, themono-, d-i-, hi, and tetraalkyl-substituted octylcyclohexano1,4-dioneand malononitrile there are obtained 2-n-octyl 1,4dicyanomethylenecyclohexane rand -eyclohexadiene. From2-isopr0pyl-1,4-cyclohexanedione and Z-tertiarybutyl-l,4-cyclohexanedione with inalononitrile, there are obtained thecorresponding 2-isopropyland Z-tertiarybutyl-l,4-dicyanomethylene-substituted cyclohexanes and cyclohexadienes.

As the degree of chain branching in the various alkyl, i.e., nionovalentsaturated, hydrocarbyl substituents, in creases and as the number ofcarbons in said substituents also increases, molecular packing factorstend to make the preparation of the compounds with increasing number ofsuch substituents more difiicult. However, within the realms of the8-carbon atom limit assigned toeach alkyl substituent on the 2-, 3-, 5-,and 6-ring carbons, it is possible to prepare tetrakis straight chainhydrocarbyl substituted compounds. More specifically, from 2,3,5,6-tetrakis-n-octyl-1,4-cyclohexanedione and malononitrile, thecorresponding 2,3,5,6-tetral;is-1,4-dicyanomethylenecyclohexane and-cyclohexadiene are obtained.

While the foregoing has been specifically directed to malononitrile asthe diacideubstituted methylene compound, the same applies asillustrated in detail in the various sections of the fioregoing ExampleI to other difunctronally substituted methylene compounds. Thus, fromdiethyl malonate, ma-lonamide, ethyl cyanoacetate, cyanolacetamide, andthe like, with the alkyl 1,4-cyclohexanediones there are obtained,respectively, the 1,4-bis(diethoxycarbonylmethylene 1,4bis(dicarbamoyl=methylene)-, 1,4-his[cyano(ethoxycarbonyl)methylene]-,1,4- bris(carbarnoylcyanomethylene) alkylcyclohexanes and-alkylcyclohexadienes. The interconversions between the variousdifunctionally substituted methylenecyclohexanes and -cyclohexadienesillustrated specifically in the various sections of foregoing Example Ilikewise apply to the just enumerated illustrative alkyl-substituted 9products of this invention. The conversion of the various products tothe bis-substituted aromatic structures, i.e., Where the bridging quinoring has been converted to a benzene ring, also similarly applies to thealkyl-substituted derivatives.

The present invention is also generic to the monoand dianiino andmonoand diether condensation products of 7,7,8,8-tetracyano pquinodirnethane and 7 ,7,8,8-tetracyanoalkyl-substituted-p-quinodimethanes and to the preparation thereof from,respectively, one and two molar proportions of the requisite aminohydrogen-bearing amine and alcoholic hydrogen-bearing alcohols andphenols, said hydroxy compounds being used in the form of their alkalimetal and alkaline earth metal salts. In the manner of U8. Patents2,762,810, -832, and -833 concerning the amino and ether condensationproducts of tetracyanoethylene, the new 7,7,8,8-tetracyanoquinodimethaneand 7,7,8,8-tetracyano-alkyl-substituted quinodimethanes likewise reactwith one to two molar proportions of amino hydrogen-bearing amines andhydroxyl hydrogen-bearing alcohols and phenols in the form of theirsalts to split out from one to two molar proportions of HCN and form thecorresponding 7-monoand 7,7-diamino and 7-monoand7,7-diether-substituted 8,8-dicyano-p-quino and-alkyl-p-quinodirnethanes, which substitution or condensation productslikewise form a specific part of the present invention. Thestoichiometry can be represented by the following four illustrativeequations, wherein R is as before, i.e., hydrogen or alkyl of up to 8carbons; M is an alkali metal or alkaline earth metal; and the Rs, whichcan be alike or different, are hydrogen, aliphatic, cycloaliphatic,aromatic, alka-romatic, aralip'natic or aralicyclic monovalenthydrocarbon radicals free of acyclic carbon-carbon unsaturation and ofany substituents carrying Zerewitinoti active hydrogen and generally ofno more than 18 carbons each. These radicals can contain heterocyclicatoms, such as oxygen, nitrogen, or sulfur, and can also be togetherjoined pairwise to form canbocyolic or heterocyclic structures Withinthe indicated limitations carrying the indicated pend ent aminohydrogenand hydroxyl hydrogen-containing sub stituents:

R R No ON o= =c +2MOR NC CN R n R a NC\ /OR o: :0 NO on n n The 7, 7, 8,8-tetracyano-p-quinodimethane and 778,8- tetracyano-alkyl-substitutedp-quinodimethanes of the present invention form charge-transfercompounds or complexes with organic and organo-inorganic Lewis bases,including specifically such Lewis base compounds carrying amino hydrogenor hydroxyl hydrogen substituents. As just stated in the immediatelypreceding section, such substituents also undergo the l-ICNcondensation-type reaction to form the also new 7-mono and 7,7-di--arninoand -ether-substituted-8,8-dicyano-p-quinoand-alkyl-pquinodimethanes. As to which will be obtained with the variousamino hydrogen and alcoholic hydrogen-bearing Lewis bases, this is, asis true of all chemical reactions, a function of the relative reactivityof the respective amino hydrogen and hydroxyl hydrogen-bearingcompounds. In many instances, both types of products will be obtainedsimultaneously, and depending upon the rigorousness of the reactionconditions applied, the equi- 00 libriurn can be shifted more to theformation of chargetransfer compounds or to the amine or ethercondensation products. In general, the charge-transfer compound willform first and the reaction can be stopped at this point by carrying itout lower temperatures or by running the reaction for only a shortperiod of time. Running the reaction at modest to elevated temperaturesor in the presence of mild to gross excesses of the amino hydrogen-andalcoholic hydrogen-containing Lewis bases will result in a tendencytoward the formation of more of the amino o-r ether condensationproducts.

Generally speaking, the reaction will be effected at modesttemperatures, most conveniently in the range of room temperature, andusually in the presence of inert diluents. Suitable such diluentsinclude, for convenience, the liquid ethers, hydrocarbons, nitriles, andamides free of Zerewitinoff active hydrogen, such as tetrahydrofuran,acetonitrile, propionitrile, dimethylformamide, dimethylacetamide, thehexanes, pentanes, and the like. The products are obtained directly bythe addition of either the tetracyanoquinodimethane to the aminohydrogenbearing or hydroXyl-bearing coreactant, the latter in salt form,or vice versa. If mono-substituted condensation products are desired,only one molar proportion of the hydrogenbearing coreactant will beused. If the disubstituted condensation products are preferred, excessesof the hydrogen-bearing coreactants will be used. The products areobtained directly at relatively short reaction times and are generalyquite intensely colored. The products can be purified by conventionalrecrystallization techniques from suitable solvents or conventionalsolution/precipitation techniques from suitable solvents and adjustedconcentrations of nonsolvents, sometimes also as a function oftemperature.

The following examples in which the parts given are by weight aresubmitted to fully ilustrate but not to limit the 7-monoand7,7-diaminoand -ether-substituted-8,8-

dicyano-p-quinoand -alkyl-p-quinodimethanes.

EXAMPLE III To a warm solution of one part of TCNQ in 88.8 parts ofanhydrous TI-IF was added 0.212 part (0.61 molar proportion based on theTCNQ) of pyrrolidine. The initially green solution turned a gray-purplecolor. The reaction mixture was allowed to stand at room temperature for17 hours, then cooled in an ice/Water bath, and

finally filtered. After air-drying, there was thus obtained 0.360 part(49% of theory) of 7,8,8-tricyano-7-pyrrolidinoquinodimethane as fine,purple-black needles which appeared to begin to melt at 233 C. and didnot melt completely up to 300 C. After recrystallization fromacetonitrile, the 7,S,8-tricyano-7-(1'-pyrrolidino)quinodimethane wasobtained as fine, purple-black needles which did not melt up to 405 0,although some blackening occurred.

Analysis-Called. for C H N C, 72.6%; H, 4.9%; N, 22.6%. Found: C, 72.9%;H, 4.7%; N, 22.5%.

The infrared spectrum showed no absorption attributable to NH. Thestrong absorption bands at 2175 and 2200 CI11. 1 are assignable toconjugated nitrile groups. The 7,8,8-tricyano-7- 1 -pyrrolidinoquinodimethane is useful as a gasoline dye in imparting a light violetcolor to white gasoline.

EXAMPLE IV To a warm solution of one part of TCNQ in 88.8 parts of THFwas added 1.7 parts (4.9 molar proportions based on the TCNQ) ofpyrrolidine. After a few minutes a yellow, crystalline compound began toprecipitate. The reaction mixture was let stand at room temperature forthree days and then cooled in an ice/water bath and filtered. Theyellow, crystalline product was washed with cold THF and then withdiethyl ether to afford 1.2 parts (84% of theory) of8,8-dicyano-7,7-di(1'-pyrrolidino)- quinodimethane as yellow crystalsmelting at 292-300 C. with decomposition. After two recrystallizationsfrom methanol, the pure 8,8-dicyano-7,7-di(1'-pyrrolidino)-quinodimethane was obtained as pale yellow crystals melting at 304-307C. with decomposition.

Analysis.-Calcd. for C H N 'C, 73.9%; H, 6.9%; N, 19.2%; N.E., 292.4.Found: C, 73.9%; H, 7.0%; N 19.0%; NE, 290.

The infrared absorption spectrum showed no absorption characteristic ofNH groups and strong absorption bands at 2175 and 2130 cmr assignable toconjugated nitrile groups.

A piece of composite cloth containing joined integral areas woven fromdifferent fibers was heated for one hour in a dye bath containing 0.02part of 8,8-dicy=ano-7,7- di(1'-pyrrolidino)quinodimethane, 200 parts ofwater, and a small amount of dimet hylformamide, and 20 parts of asolution of a commercial dispersing agent. At the end of this dyeingcycle the cloth was removed and waterwashed. The silk, wool, and nylonportions of the composite cloth were dyed yellow. This color was fast tosoaping.

EXAMPLE V To a mixture of 0.5 part of7,8,8-tricyano-7-(1'-pyrrolidino)quinodimethane and 35.5 parts of THEwas added 0.851 part of pyrrolidine. Tie reaction mixture turned green,and yellow crystals slowly began depositing therefrom. The reactionmixture was let stand five hours under room temperature and the yellow,crystalline prodnot isolated by filtration. After washing with diethylether and drying, there was thus obtained 0.465 part (80% of theory) of8,8-dicyano-7,7-di(1'-pyrrollidino)- quinodimethane as yellow crystalsmelting at 276- 281 C. with decomposition. After recrystallization frommethanol, the pure 8,8-dicyano-7,7-di(1-pyrrolidino)qutinodimethane wasobtained as yellow crystals melting at 289.5-311 C. with decomposition.Mixed melting point with the dicyanodipyrrolidinoquinodimethane obtaineddirectly from TCNQ and pyrrolidine was 286.5-299.5 C. withdecomposition, thus showing the products to be identical. The infraredspectrum of the product from pyrrolidine and thetricyanopyrrolidinoquinodimethane was also substantially identical withthat of dicyanodipyrrolidinoquinodimethane.

- 12 EXAMPLE vi To a warm solution of two parts of TCNQ in 222 parts ofTHF was added 0.89 part (1.25 molar proportions based on the TCNQ) ofn-butylamine. The resultant dark solution was let stand at roomtemperature for 48 hours and then concentrated at reduced pressure to adark solid. This was dissolved in dilute aqueous sodium hydroxidesolution and undissolved material removed by filtration. The filtratewas washed with about one part of a 1:1 by volume pen-tane/diethyl ethermixture and the deep red, aqueous layer was taken. After acidificationwith dilute aqueous hydrochloric acid solution, the resultant darkpurple precipitate was removed by filtration, washed with water, anddried. There was thus obtained two pants (82% of theory) of7-n-butylarnino- 7,8,8-tricyanoquinodimethan e as purple crystals. Theproduct was purified by dissolving it in THF and reprecipitationthere-from by careful addition of n-hexane. There was thus obtained 1.44parts of pure product as a purple powder melting at 159169.0 C.

Analysis.Calcd. for C H N C, 72.0%; H, 5.6%; N, 22.4%; M.W., 246. Found:C, 71.6%; H, 5.7%; N, 21.8%; M.W., 232, 247.

The infrared spectrum exhibited absorption in a region characteristic ofthe N-H linkage and showed a triplet in the nitrile region. Theultraviolet and visible spectra exhibited absonption at 262 millimicronsand weaker absorption from 425 to 617 millimicrons. These spectral dataare consistent with the view that the product is a mixture of thetautorners 7-n-butylamino-7,8,8-tricyanoquinodimethane anda,ot',ot'-tricyano-a N butylimino-p- Xylene.

EXAMPLE VII To a solution of 0.125 part of a mixture of 4.28 parts ofTCNQ and 1.455 parts of pphenylenedimalononitrile (dihydro TCNQ) in 13.3parts of THF was added 0.11 part (3.0 molar proportions based on themethane) of n-butylamine. The reaction mixture immediately turned deepred and was allowed to stand under nitrogen at room temperature for 18hours. The crystalline solid was removed by filtration and washed withtetrahydro- 'fura-n. On drying, there was thus obtained 0.110 part oftheory) of crude 7,7-bis(n-butylamino) 8,8-dicyanoquinodimethane as dullred crystals me ltintg at 261- 263 C. with decomposition. The solid wastaken up in boiling methanol, treated with decolorizing charcoal,filtered, and the purified product precipitated with diethyl ether. Thepale yellow crystals thus obtained melted at 264266 C. withdecomposition. Further recrystallization from methanol/water affordedpure 7,7-bis(n-butylamino)-8,S-dicyanoquinodimethane as pale yellowcrystals melting at 270275 C. with decomposition.

Analysis.Cal=cd. for C H N C, 72.9%; H, 8.2%; N, 18.9%. Found: C, 72.7%;H, 8.2%; N, 18.8%.

EXAMPLE VIII To a warm solution of :two parts of TCNQ in 266 parts ofTHF was added 2.92 parts (4.1 molar proportions based on the TCNQ) ofn-butylamine. The mixture was allowed to stand at room temperature for24 hours and the solid removed by filtration. The filter cake was washedwith diethyl ether and dried. There was thus obtained 2.35 parts (81% oftheory) of 7,7- bis(n butylamino)-8,8adicyanoquinodimethane as yellowcrystals melting at 270-273 C. with decomposition.

Analysis.Calcd. for C I-I N NE. 296. Found: N.E., 300.

EXAMPLE IX To a solution of four parts of TCNQ in 311 parts of THE wasadded a solution of 1.26 parts (3.8 molar proportions based on the TCNQ)of ammonia in 200 parts of tetrahydrofuran. The resultant dark liquidreaction mixture was stored at room temperature for 69 hours undernitrogen. Upon filtration at the end of this period there was obtained3.02 parts (82% of theory) of 7,7- diamino 8,8 di cyanoquinodimethane asa yellow'brown solid. A portion of the product was twice recrystallizedfrom a mixture of dimethylforrnamide and THE to afford pure 7,7-diamino8,8 dicyanoquinodimethane as yellow microcrystals which turned brown at368 C. but did not melt up to 400 C.

Analysis.-Calcd. for C H N C, 65.2%; H, 4.4%; N, 30.4%. Found: C, 65.4%;H, 4.6%; N, 30.5%.

The 7,7-diamino-8,8-dicyano product was still further characterized byhydrolysis under alkaline conditions to homoterephthalic acid, whichwould not be possible for the isomeric 7,8-diamino-7,8-dicyano compound.

A mixture of one part of the above 7,7-diamino-8,8-dicyanoquinodimethane, six parts of sodium hydroxide, and 25 parts ofWater was refluxed with stirring for five hours. The reaction mixturewas then cooled and acidified with dilute hydrochloric acid. Uponfiltration there was thus obtained 0.230 part of crude homoterephthalicacid as a light tan solid melting at 225230 C. Recrystallization fromdiethyl ether afforded pure homotere-p'hthalic acid as a white solidmelting at 23 6 237 C. The mixed melting point with authentichomoterephthali-c acid of melting point 241.5242 C. was 239241 C. Theinfrared spectrum of the hydrolyzed product is identical with that ofthe separately obtained sample of homoterephthalic acid.

EXAMPLE X To a mixture of 0.3 part of 7,8,8tricyano-7-(l-pyrrolidino)quinodimethane in 220 parts of THF was added 0.74 part of n-butylamine.The reaction mixture was let stand four hours at room temperature andthe solid product removed by filtration. There was thus obtained 0.18part of crude 7-n-butylamino 8,8dicyano-7-(1-pyrr0lidino)q-uinodimethane as a pale yellow soiid meltingat 105134 C. with decomposition. After recrystallization fromacetonitrile the pure 7-n-butylamino-8,8-dicyano-7-(1'-pyrrolidino)quinodimethane was obtained as pale yellow crystalsmelting at 267269 C. with decomposition.

Analysis.Calcd. for C H N C, 73.4%; H, 7.5%; N, 19.0%. Found: C, 73.6%;H, 7.4%; N, 19.4%.

The same product was obtained by adding 0.085 part of py-rrolidine to amixture of 0.08 part of 7-n-butylamino- 7,8,8-tricyanoquinodi-methane in8.88 parts ocE THE. A precipitate formed immediately. The reactionmixture was let stand for 21 hours at room temperature and the solidthen removed by filtration. The filter cake was washed with diethylether to afford 0.07 part of7-n-butylamino-8,8-dicyano-7-(1-pyrrolidino)quinodimethane as ayellow-red solid. After recrystallization from an acetonitrile/diethylether mixture, there was thus obtained 0.02 part of pure7-n-butylamino-8,8dicyano-7-(1'-pyrroiidino)quinodimethane as pale pinkcrystals melting at 261262 C. with decomposition. A mixed melting pointwith the preceding product showed no depression (259.5- 264 C. withdecomposition). The intrared spectra of the two products were alsoidentical.

EXAMPLE XI To a mixture of 0.5 part of7,8,8-tricyano-7-(1'-pyrrolidino)quinodimethane and 13.3 parts of THEwas added 8.88 parts of THF saturated with dry ammonia. The mixture wasstirred for minutes and then allowed to stand at room temperature fortwo hours. After cooling in an ice/Water bath, the yellow-tan crystalsof crude 7- amino-8,8-dicyano-7(1'-pyrrolidino)quinodimethane wereremoved by filtration. After drying, there was thus obtained 0.465 part(98% of theory) of the aminodicyanopyrrolidinoquinodimethane. After tworecrystallizations from a mixture of dimethylformamide and diethylether,

1a the pure 7-amino-8,8-dicyano-7( l-pyrrolidino) quinodimethane wasobtained as yellow microcrystals melting at 308.5310 C. withdecomposition.

Analysis.Calcd. for CMHMNQ C, 70.6%; H, 5.9%; N, 23.5%. Found: C, 70.5%;H, 6.1%; N, 23.9%, 24.1%.

EXAMPLE XII To a solution of the two parts of TCNQ in 169 parts of THFwas added 17.8 parts of THF containing 2.43 parts (5.5 molar proportionsbased on the TCNQ) of dimethylamine. The resulting solution was allowedto stand at room temperature for 17 hours and was then concentrated invacuo to one quarter the original volume. The concentrate was diluted50% by volume With diethyl ether and the resultant reaction mixturefiltered. There was thus obtained 1.75 parts (74% of theory) of7,7-bis(dimethylamino)-8,8-dicyanoquinodimethane as yellow crystalsmelting at 213-232 C. with decomposition. Recrystallization from amixture of methanol and diethyl ether followed by recrystalization froma mixture of acetonitrile and diethyl ether attorded the purified7,7-bis(dimethylamino)-8,8-dicyanoquinodimethane as yellow-orangecrystals melting at 232-236 C. with decomposition.

Analysis.-Calcd. for C I-1 M C, 70.0%; H, 6.7%; N, 23.3%. Found: C,70.0%; H, 7.0%; N, 23.2%, 23.5%.

EXAMPLE XIII To a solution of two parts of TCNQ in 169 parts of THF wasadded a solution of 2.53 parts of THF containing 0.346 part (1.26 molarproportions based on the TCNQ) of dimethylamine. The solution turneddark green, and after one hour at room temperature dark crystals beganto form. The reaction mixture was let stand for 20 additional hours atroom temperature under nitrogen and the resulting purple mixturefiltered to afford 0.765 part of crude product. After recrystallizationfrom acetonitrile, the mixed 2/1 TCNQ/dimethylammonium anion radical and7-dimethylamino-7,8,S-tricyanoquinodimethane product were obtained asblack crystals. Acetonitrile solutions of the crystaliine productexhibited the characteristic absorption in both the ultraviolet andvisible spectra for the TCNQ radical-anion (394, 740, and 840millimicrons) and in addition showed absorption at 578 millimicronsascribable to the presence of 15-20% of the7-dimethylamino-7,8,8-tricyanoquinodimethane.

XAMPLE XIV To a hot solution of one part of TCNQ in 54.8 parts ofacetonitrile was added 7.22 parts (14.7 molar proportions based on theTCNQ) of diisopropylamine. The solution was allowed to stand undernitrogen for three days at room temperature and an aliquot takentherefrom for ultraviolet spectral analysis. The sample exhibited strongabsorption in the range 415, 740, and 840 millimicrons characteristicfor the 2/1 TCN-Q/amine radical-anion charge-transfer compounds, i.e.,here for the 2/1 TCNQ/diisopropylammonium compound. In addition, therewere also absorption bands at 223 millimicrons and at 320 millimicrons,which bands are characteristic for the bis-aminodicyanoquinodimethanesubstitution products, i.e., in this intsance for7,7-bis(diisopropylamino)-8,8-dicyanoquinodimethane.

EXAMPLE XV To a mixture of 0.25 part of7,8,8-tricyano-7-(1'-pyrrolidino)quinodimethane, 3.9 parts ofacetonitrile, and 0.94 part of dimethylformamide was added dropwise withstirring hydrazine hydrate until a homogeneous yellow solution wasobtained (about .06 part required). A large volume of diethyl ether wasadded and the supernatant liquid decanted from the resultant orange oilwhich separated. Trituration of the-oil in the presence of acetonitrile,coupled with scratching, caused the oil to solidify. There was thusobtained 0.182 part (73% of theory) 8,8-dicyano 7hydrazino-7-(1-pyrrolidino)quinodimethane as an orange-yellow solidmelting at 2052tl0- C. with decomposition. On precipitation from asolution of dimethylformamide containing a small amount of acetonitrileby addition of diethyl ether, the purifieddicyanohydrazinopyrrolidinoquinodimethane was obtained as pale yellowmicrocry-sta'ls melting at 2l7223 C. With decomposition.

Analysis.-Calcd. for C H N C, 66.4%; H, 6.0%; N, 27.6%. Found: C, 66.2%;H, 6.0%; N, 28.1%.

An aqueous solution of the 8,8-dicyano-7-hydrazino-7-pyrrolidinoquinodimethane dyed wool, silk, and nylon yellow fast tosoaping.

EXAMPLE XVI A mixture of one part of TCNQ, three parts (5.0 molarproportions based on the TCNQ) of p-anisidine, 59' parts ofacetonitrile, and 24.8 parts of pyridine was refluxed under anatmosphere of nitrogen for one hour and then allowed to stand undernitrogen at room temperature for 22 hours. The reaction mixture wasconcentrated in vacuo, and the resultant solid residue was suspended indiethyl ether and filtered. After drying, there was obtained 1.41 parts(73% of theory) of 7,7-bis(p-anisidino)- 8,8-dicyanoquinodimethane asdark crystals melting at 292298 C. After repeated precipitation fromdimethylformamide solution by addition of diethyl ether, the purifiedproduct was obtained as yellow crystals melting at 288-294 C. withdecomposition.

Analysis.-Calcd. for C H O N C, 72.7%; H, 5.1%; N, 14.1%. Found: C,72.9%; H, 5.2%; N, 13.8%.

EXAMPLE XVII yellow solid melting at 231257 C. with decomposition.

Precipitation from ethanol solution containing a small amount of diethylether by addition of n-hexane and from acetonitrile solution by additionof diethyl ether afforded the pure7,7-bis(benzylamino)-8,8-dicyanoquinodimethane as yellow crystalsmelting at 244246 C. with decomposition.

Analysis.Calcd. for C H N C, 79.1%; H, 5.5%; N, 15.4%. Found: C, 78.9%;H, 5.7%; N, 15.7%.

EXAMPLE XVIII To a warm solution of one part of TCNQ in 47 parts ofacetonitrile was added 0.4 part (1.36 molar proportions) ofethylenediarnine. A green color formed, and a precipitate began to formimmediately. After standing for 1.5 hours at room temperature, themixture was filtered giving 0.927 part (90% of theory) of yellow-greensolid 7,7 ethylenediamino 8,8 dicyanoquinodimethane which can also benamed 2-(4-dicyanomethylenecyclohexa-2,5-dienylidene)imidazoline.Precipitation from dimethylformamide solution by the addition of ethergave a purified yellow solid product which did not melt up to 405 C.

Analysis.Calcd. for C I-I N; C, 68.6%; H, 4.8%; N, 26.7% ,Found: C,68.1%; H, 4.8%.

16 EXAMPLE XIX A mixture of 0.57 part of7,8,8-tricyano-7-(1-pyrrolidino)quinodimethane, 35.6 parts of methanol,and a catalytic amount of sodium methoxide was heated at steam bathtemperatures until a yellow-red solution was formed. The solution wasfiltered and the solvent evaporated from the filtrate in vacuo.Cyclohexane containing a small amount of diethyl ether was then added tothe residue and the resultant precipitate removed by filtration. Therewas thus obtained 0.277 part (48% of theory) of 8,8-dicyano-7-methoxy-7-1-pyrrolidino) quinodirnethane as yellow crystals. After tworecrystallizations from an about /2 part by volume acetone/diethyl ethermixture, the purified dicyanomethoxypyrrolidinoquinodimethane wasobtained as yellow crystals melting at 128129 C. turning blood-red atthe melting point.

Analysis.-Calcd. for C H N O: C, 71.1%; H, 6.0%; N, 16.6%. Found: C,71.4%; H, 6.0%; N, 16.3%, 16.6%.

The ultraviolet spectrum of the product exhibited characteristicabsorption at 222 and 402 millimicrons. The infrared spectrum showedabsorption at 2180- and 2140 cm. characteristic of conjugated nitrilegroups. There was no absorption characteristic of OH or NH groups.

EXAMPLE XX To a stirred solution of 0.54 part of sodium methoxide in79.3 parts of methanol was added rapidly under nitrogen a solutino ofone part of TCNQ in 102 parts of THF. The reaction mixture was let standfor one half-hour at room temperature and the orange solution thenconcentrated in vacuo to an oily residue. THF (88.8 parts) was addedwith stirring and the resultant precipitate removed by filtration. Thefiltrate was concentrated in vacuo to an orange oil which on treatmentwith diethyl ether solidified. Upon filtration there was obtained 0.7part (67% of theory) of 8,8-dicyano-7,7-dimethoxyquinodimethane as ahygroscopic orange solid. The infrared spectrum of the product showsabsorption at 2190 and 2130 CIIIII, characteristic of the conjugatednitrile function and is wholly in accord with the8,8-dicyano-7,7-dimethoxyquinodimethane structure.

EXAMPLE XXI To a stirred solution of 0.681 part of sodium ethoxide in78.9 parts of ethanol was added a solution of one part of TCNQ in 88.8parts of the THF over a period of 15 minutes under nitrogen. Thereaction mixture was stirred at room temperature for an additional hour,and the green solution was then concentrated in vacuo to a brown gumwhich solidified on scratching in the presence of a THF/diethyl ethermixture. The resulting brown solid was heated to the reflux with 134parts of THF and the resultant mixture filtered. The filtrate wasconcentrated in vacuo, giving a tan-green oil which solidified onscratching in the presence of a THE/diethyl ether mixture. Uponfiltration there was obtained 0.87 part (73% of theory) of8,S-dicyano-7,7-diethoxyquinodimethane as a yellow-tan solid melting at187-200" C. with decomposition. The infrared spectrum of the productshowed absorption at 2190 and 2140 cm. characteristic of conjugatednitrile groups, and at 1675 cmf characteristic of the C=C(OR) group, at1605 cm. characteristic of the C=C(CN) group, and at 1080 cm?characteristic of the COC group.

EXAMPLE XXII To a warm solution of one part of TCNQ in 47 parts ofacetonitrile was added 0.336 part (1.1 molar proportion based on TCNQ)of ethanolamine. Crystals began to precipitate almost at once. Afterstanding 2.5 hours at room temperature, the mixture was filtered giving0.570 part (55% of theory) of yellow-green crystals of 2-(4-dicyanomethylenecyclohexa-2,5 dienylidene) oxazolidine,

which did not melt up to 400 C. although extensive reddening occurs.Recrystallization from dimethylformamide-ether with the help ofdecolorizing charcoal give bright yellow microcrystals which did notmelt up to 400 C.

Analysis.Calcd. for C H N O: C, 68.2%; H, 4.3%; N, 20.0%. Found: C,68.1%; H, 4.2%; N, 19.7%.

EXAMPLE XXIII To a warm solution of one part of TCNQ in 77 parts ofacetonitrile was added five parts (5.5 molar proportions based on TCNQ)of n-dodecylamine. The mixture was let stand at room temperature forthree days and then filtered to give 2.37 parts (90% of theory) of waxyyellow 7,7-bis(dodecylamino)-8,S-dicyanoquinodimethane, MI. 188206 C.with decomposition. Two recrystallizations from acetonitrile afiordedthe purified product, M.P. 214216 C. with decomposition.

Analysis.Calcd. for C H N C, 78.4%; H, 10.8%; N, 10.8%. Found: C, 78.3%;H, 10.9%; N, 10.6%.

EXAMPLE XXIV To a mixture of one part of7,8,8-tricyano-7-(1-pyrrolidino)quinodimethane and 12 parts ofacetonitr-ile was added approximately two parts of hydrazine hydrate.The resulting solution was treated with a large volume of ether, and theprecipitated oil was separated and scratched in the presence of a 1/1mixture of ether and acetonitrile which caused solidification.Filtration gave 0.560 part of orange solid which on recrystallizationfrom dimethyl'fonnamide-ether gave 0.470 part of yellow solid whichturns red at 215 C. but did not melt up to 400 C. Recrystallization fromdimethylacetamide-ether afforded the pure7,7-bishydrazino-8,8-dicyanoquinodimethane as a yellow solid which didnot melt up to 400 C.

Analysis.-Calcd. for C H N z C, 56.1%; H, 4.7%; N, 39.2%. Found: C,56.3%; H, 5.1%; N, 38.0%.

The infrared spectrum showed strong N-H absorption at 3300 and 3200(JUL-1 and at 1680 omf conjugated CEN at 2175 and 2125 cmr' and no CHabsorption at 14601470 cmf As illustrated in the foregoing specificexamples, a wide variety of amino hydrogen-bearing amines and hydroxy]hydrogen-bearing hydroxy compounds can be used in preparing the aminoandether-substituted tricyanoand dicyanoquinodimethanes of the presentinvention. Also as illustrated in these specific examples, mixed typecompounds likewise fall within the purview of the invention, i.e.,7,7-di-substituted-8,8-dicyanoquinodimethanes, wherein one of the7-substituents is an amino substituent and the other is an ethersubstituent. These mixed substituents can likewise be together joined.Also as illustrated in the foregoing examples, mixed disubstituted aminoand ether compounds, wherein two diiferent amino or ether substituentsare present in the same molecule, also form part of the presentinvention. These mixed disubstituted amino and ether compounds can, ofcourse, be obtained by reaction of equimolar proportions of the twodifferent amino hydrogen-containing or hydroxyl hydrogen-containingcoreactants with one molar proportion of the tetnacyanoquinodimethane.However, using such techniques it is obvious that mixtures of the twosymmetrical disubstituted compounds with the desired mixed disubstitutedcompound will be obtained. If such mixed disubstituted products aredesired, it will be preferred, as illustrated in these examples, thatone molar proportion of one of the coreactants be reacted with one molarproportion or thereabouts of the tetracyanoquinodimethane to prepare asan intermediate the 7monosubstituted 7,8,8-tricyanoquinodimethane whichwill then be reacted with one molar proportion of the second aminohydrogenor hydroxy hydrogen-containing requisite coreactant to form thedesired mixed disubstituted product.

In addition to the foregoing detailed examples, fuither specificexamples of the amino hydrogen-bearing and hydroxy hydrogen-bearingcoreactants for reaction with tetracyanoquinodimethane and theallryl-substituted tetracyanoquinodimethanes and the products obtainedtherefrom using the technique just specifically described are found inthe following list where R is as before, i.e., hydrogen or monovalentsaturated aliphatic hydrocarbon radical (alkyl) of no more than eightcarbons:

Coreactant Product R R NO H 2N(CH2)3NH2 /O: :0

No g

No i i HO 9 m /O (OII2)3OH C: :0

NC/ W \O NH R R 01130 NH; CHSO I ON CHO NH C :0

3 2 CHSO \CN NH R R o R R CIIJO- OH CHKO /CN C =0 0H30 OH I CN 0 R R R RNo O IIOCHZOH /o= =c No \O Coreactant Product NC OCHzCIIzNRz RzNCHzCHzOOCHgCHgNRz RzNCHzCI-IzOH R R R R l l l R R R R Y n NC CN NC CN In allthe foregoing primary amines, i.e., those carrying one or more NHsubstituents, one of the hydrogens on one or all of the said NHsubstituents can be replaced by a radical R of the type discussedpreviously in the stoichiometry, which radical R can be alike ordifferent to the radical on which the said NI-I substituent is alreadypendent in the case of the primary amines.

As illustrated in the foregoing detailed examples, the monoand diarninoand ether or mixed amino ether condensation products oftetracyanoquinodimethane are generically colored compounds tendingtoward the deep shades which are generically useful as dyes, forinstance, as gasoline dyes, as well as dyes for use in coloringtextiles, threads, fabrics, and the like, by conventionally used dyeingtechniques.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. Compounds represented by the formula R1000 CHr-CI-Iz COORi /C=O /C=CR 0 O OH2CH2 C O 0 R1 wherein R is a hydrocarbyl radical of from 1 to 30carbons and free of aliphatic unsaturation.

3. Compounds represented by the formula wherein R and R are hydrocarbylradicals of from 1 to 30 carbons and free of aliphatic unsaturation. 4.Compounds represented by the formula wherein X is halogen.

5. 1,4-bis (dicyanomethylene) cyclohexane. 6.1,4-bis(dicyanomethylene)-2-1nethylcycloheXane. 7. Compounds representedby the formula II n R1000 1:0 0001a 0:0 0:0 R1O0C/ 0:0 oooal 11 l1wherein R is a hydrocarbyl radical of from 1 to 30 carbon atoms and freeof aliphatic unsaturation.

8. Compounds represented by the formula wherein R and R are hydrocarbylradicals of from 1 to 30 carbons and free of aliphatic unsaturation. 9.Compounds represented by the formula wherein X is halogen.

10. 1,4-bis dicyanomethylene cyclohexadiene.

11. 1,4 bis(dicyanomethylene) Z-methylcyclohexadiene.

12. Process for preparing 1,4-bis(bisubstitutedmethylene)cyclohexadienecompounds of the formula wherein Q Q Q and Q are members of the classconsisting of COOR CONR R COX, and CN, where R R and R are selected fromthe group consisting of hydrogen and hydrocarbyl radicals of from 1 to30 carbons and free of aliphatic unsaturation, and X is halogen, and Yis a member of the class consisting of 1,4-cyclohexadienediylidene andalkyl-substituted 1,4-cyclohexadienediylidene groups, said alkylradicals being of from 18 carbons, which comprises reacting, in thepresence of a catalyst, said catalyst being a member of the classconsisting of acids, bases and salts which ionize in water to giveacidic or basic solutions, a member of the class consisting of1,4-cyclohexanedione and alkyl-substituted 1,4-cyclohexanediones, saidalkyl radicals being of from 1-8 carbons, with from 1 to 2disubstitutedmethylene compounds having the formulas wherein the Qs havethe same significance as above, and isolating the 1,4-bisdisubstitutedrnethylene cyclohexane compound, which compound is thenoxidized by halogenation/dehydrohalogenation reactions to the said1,4-bis (disubstitutedmethylene)cyclohexadiene compound.

13. Compounds of the formula R R No l Y /C: :C\ No Z wherein Y and Z aremembers of the class consisting of CN, NR R and O'R radicals, Y and Zbeing alike or different, except that no more than one of Y and Z iscyano; R and R are members of the class consisting of hydrogen andmonovalent hydrocarbon radicals of 1 to 18 carbon atoms free ofaliphatic unsaturation; and R is a member of the class consisting ofhydrogen and alkyl hydrocarbon radicals of from 1 to 8 carbon atoms.

14. Process for preparing compounds of claim 13 which comprises reactinga member of the class consisting of 7,7,8,8-tetracyano-p-quinodimethaneand 7,7,8,8-tetracyano alkyl-substituted p-quinodimethanes, said alkylradicals being of from 1-8 carbons, with from 1 to 2 molar proportionsof a compound of the group consisting of R R NH wherein R and R aremembers of the class consisting of hydrogen and monovalent hydrocarbonradicals of 1 to 18 carbon atoms free of aliphatic unsaturation and MORReferences Cited in the file of this patent UNITED STATES FATE T S I. ofOrganic Chemistry, vol. 20, pages 13-32 (1955) (Talukdar et al.).

Bailar: Chemistry of the Coordination Compounds, pages 556-8 (1958).

1. COMPOUNDS REPRESENTED BY THE FORMULA
 13. COMPOUNDS OF THE FORMULA